Arylation of hydrocarbons enabled by organosilicon reagents and weakly coordinating anions.
| Autor: | Shao B; Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA., Bagdasarian AL; Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA., Popov S; Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA., Nelson HM; Department of Chemistry and Biochemistry, University of California, Los Angeles, CA 90095, USA. hosea@chem.ucla.edu. |
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| Jazyk: | angličtina |
| Zdroj: | Science (New York, N.Y.) [Science] 2017 Mar 31; Vol. 355 (6332), pp. 1403-1407. |
| DOI: | 10.1126/science.aam7975 |
| Abstrakt: | Over the past 80 years, phenyl cation intermediates have been implicated in a variety of C-H arylation reactions. Although these examples have inspired several theoretical and mechanistic studies, aryl cation equivalents have received limited attention in organic methodology. Their high-energy, promiscuous reactivity profiles have hampered applications in selective intermolecular processes. We report a reaction design that overcomes these challenges. Specifically, we found that β-silicon-stabilized aryl cation equivalents, generated via silylium-mediated fluoride activation, undergo insertion into sp 3 and sp 2 C-H bonds. This reaction manifold provides a framework for the catalytic arylation of hydrocarbons, including simple alkanes such as methane. This process uses low loadings of Earth-abundant initiators (1 to 5 mole percent) and occurs under mild conditions (30° to 100°C). (Copyright © 2017, American Association for the Advancement of Science.) |
| Databáze: | MEDLINE |
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